EP0384091A1 - Glycerolderivate, ihr Herstellungsverfahren, diese enthaltende vernetzbare Zusammensetzungen und ihre Anwendung in der Textilindustrie - Google Patents

Glycerolderivate, ihr Herstellungsverfahren, diese enthaltende vernetzbare Zusammensetzungen und ihre Anwendung in der Textilindustrie Download PDF

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Publication number
EP0384091A1
EP0384091A1 EP89403447A EP89403447A EP0384091A1 EP 0384091 A1 EP0384091 A1 EP 0384091A1 EP 89403447 A EP89403447 A EP 89403447A EP 89403447 A EP89403447 A EP 89403447A EP 0384091 A1 EP0384091 A1 EP 0384091A1
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EP
European Patent Office
Prior art keywords
propanol
glyoxyloyloxy
ppm
general formula
crosslinking
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89403447A
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English (en)
French (fr)
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EP0384091B1 (de
Inventor
Didier Wilhelm
Fernand Cuirassier
Alain Blanc
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanofi Aventis France
Original Assignee
Francaise Hoechst Ste
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Publication date
Application filed by Francaise Hoechst Ste filed Critical Francaise Hoechst Ste
Priority to AT89403447T priority Critical patent/ATE91484T1/de
Publication of EP0384091A1 publication Critical patent/EP0384091A1/de
Application granted granted Critical
Publication of EP0384091B1 publication Critical patent/EP0384091B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate

Definitions

  • the present invention relates to new glycerol derivatives, their preparation process, their use as crosslinking agents, crosslinking or crosslinkable compositions containing them and their use in the textile industry.
  • Copolymers capable of being insolubilized by crosslinking have been known for a long time.
  • This crosslinking is generally obtained by introducing into the mixture of the monomers to be copolymerized a monomer comprising one or more reactive groups such as a carboxyl, vinyl, hydroxyl, oxirane, optionally substituted carbamoyl group, optionally etherified carboxyhydroxymethyl, such as for example N -methylolacrylamide, acrylamidoglycolic acid, methylenebisacrylamide, 1,2-diacryloylamino-1,2-dihydroxy-ethane, tetraallyloxyethane, glycidyl methacrylate.
  • reactive groups such as a carboxyl, vinyl, hydroxyl, oxirane, optionally substituted carbamoyl group, optionally etherified carboxyhydroxymethyl, such as for example N -methylolacrylamide, acrylamidoglycolic acid, methylenebisacrylamide, 1,2-diacryloy
  • copolymers can be crosslinked by simple heating, generally in the presence of an acid catalyst or capable of releasing an acid, this is the case, for example, of acrylic, vinyl or acrylovinyl copolymers containing as crosslinking agent methylol amides of unsaturated organic acids such as acrylic acid, maleic methacrylic acid.
  • crosslinking monomers have the property of releasing, either during their polymerization or during their crosslinking, traces of formaldehyde, the drawbacks of which are known today; others are either insoluble in water, or not very reactive, or difficult to incorporate into the desired copolymer.
  • the object of the present invention is in particular to provide new crosslinking agents which overcome these drawbacks.
  • the new crosslinking agents according to the present invention are the glycerol derivatives of general formula (I): in which R represents an allyl, methylallyl, acryloyl or methacryloyl group and R1 and R2 are identical, represent a glyoxyloyl group, or different, represent a hydrogen atom or a glyoxyloyl group.
  • a more particular subject of the invention is the glycerol derivatives as defined above, characterized in that in said formula (I), R represents an allyl, acryloyl or methacryloyl group and R1 and R2 retain the meaning given above.
  • the subject of the invention is in particular: - acryloyloxy-3 glyoxyloyloxy-2 propanol-1; - 1-acryloyloxy-3-glyoxyloyloxy-propanol-2; - acryloyloxy-1 diglyoxyloyloxy-2,3 propane; - methacryloyloxy-3 glyoxyloyloxy-2 propanol-1; - methacryloyloxy-1 glyoxyloyloxy-3 propanol-2; - methacryloyloxy-1 diglyoxyloyloxy-2,3 propane; - allyloxy-3 glyoxyloyloxy-2 propanol-1; - allyloxy-1 glyoxyloyloxy-3 propanol-2.
  • the derivatives of general formula (I) above can be prepared by a process characterized in that the glyoxylic acid is reacted with a substituted oxirane of general formula (II) in which R has the meaning indicated above, to obtain a product of general formula (I) such as defined above:
  • the process described above is carried out as follows: The reaction of glyoxylic acid with the substituted oxirane of general formula (II) is carried out: . at a temperature between 50 ° C and 120 ° C, advantageously around 80 ° C; . with an excess of substituted oxirane of general formula (II); .
  • glyoxylic acid in aqueous solution advantageously with an aqueous solution of glyoxylic acid at 75 ⁇ 10% by weight; . in the presence of a catalyst is derived from chromium such as chromium acetylacetonate, or is preferably basic such as a tertiary amine such as triethylamine or dimethyllaurylamine; optionally in the presence of a solvent such as an aliphatic or aromatic hydrocarbon, such as ...; . by eliminating at the end of the reaction the excess of the substituted oxirane used by washing the reaction medium diluted with water with a compatible organic solvent, immiscible with water, preferably diethyl ether.
  • a catalyst is derived from chromium such as chromium acetylacetonate, or is preferably basic such as a tertiary amine such as triethylamine or dimethyllaurylamine; optionally in the presence of a solvent such as an ali
  • the product of general formula (I) can be identified by the preparation of a derivative characteristic of its aldehyde function (s) such as oxime, O-methyl oxime, phenylhydrazone, dinitrophenylhydrazone according to the usual methods for preparing these derivatives.
  • a derivative characteristic of its aldehyde function such as oxime, O-methyl oxime, phenylhydrazone, dinitrophenylhydrazone according to the usual methods for preparing these derivatives.
  • O-methyl oxime obtained by reacting in aqueous medium, an excess of methoxyamine hydrochloride on the reaction crude which has been eliminated. , beforehand, the untransformed starting oxirane. O-methyl oximes thus obtained can be purified by means known per se such as distillation, chromatography, etc.
  • the present application also relates to the use of derivatives of general formula (I) as defined above as crosslinking agents.
  • the derivatives of formula (I) according to the invention can advantageously enter into a crosslinking and / or crosslinkable composition, containing at least one glycerol derivative as defined above copolymerizable with at least one monomer copolymerizable with this derivative.
  • this glycerol derivative of an ethylenic bond allows its polymerization or its copolymerization with other monomers while retaining its crosslinking activity. It is likely that the glyoxyloyl group (s) present in this glycerol derivative react on the hydroxyl groups of the polymers or copolymers formed to form acetal bridges and thus crosslink the macromolecules, as will be shown below, the composition according to the invention behaves differently from a simple mixture.
  • the monomers which can be copolymerized with a derivative of formula (I) according to the invention to give copolymers which can themselves enter into a crosslinking reaction include acrylic or methacrylic monomers such as acrylates and methacrylates of C1-C18 alkyl, vinyl ethers and esters such as vinyl acetate, vinyl propionate, vinyl chloride, (meth) acrylic acid, and its alkali metal or ammonium salts, acrylonitrile, styrene or substituted olefins such as vinylsulfonic acid, preferably salified in the form of sodium salt. Mixtures of these monomers can also be used.
  • This copolymerization of the glycerol derivative of general formula (I) with other unsaturated monomers can be carried out in dispersion, in emulsion, in solution either by a batch process, or by semi-continuous or continuous processes, according to known means, in the presence of one or more polymerization initiators such as a Redox system, an azo, a peroxide and / or a hydroperoxide.
  • the proportion of the crosslinking agent introduced into the copolymer can vary in large proportions from 0.1 to 15% by weight, preferably from 0.5 to 5% by weight relative to the total weight of the monomers used.
  • the crosslinking and / or crosslinkable copolymers are obtained by copolymerizing the glycerol derivative used as a crosslinking agent previously prepared.
  • the choice of monomers used in the copolymerization makes it possible to modify certain physical properties of the substances obtained after crosslinking, such as flexibility, hardness, coloring.
  • the introduction into the copolymer of reactive groups such as hydroxyl, carboxyl, carbamoyl or other groups, can usefully reinforce the crosslinking properties.
  • the crosslinking effect can also be reinforced by adding known catalysts such as acids, ammoniacal salts or salts of mineral or organic acids of metals having several valences, such as, for example, chlorides, magnesium nitrates, zinc, calcium, aluminum, zirconium.
  • crosslinking and / or crosslinkable compositions according to the invention the property of these compositions has been demonstrated to give films resistant to organic solvents by simple heating. Heating produces crosslinking within the macromolecules of the copolymer or between the macromolecules of the copolymer.
  • compositions of the invention make them more particularly interesting in the textile industry or in the paper industry.
  • These compositions can in fact be used for making fiber masts or nonwovens or for improving the effects of treatments to make the fabrics wrinkle-resistant. They make it possible in particular to obtain fabrics, woven or non-woven, which are resistant to organic solvents, in particular to organic solvents used in dry cleaning operations and to increase the abrasion resistance and wrinkle resistance as well as the permanent washing of treatments intended to make the fabrics wrinkle-free; they therefore make it possible to obtain wrinkle-resistant fabrics thanks to the treatment of a fabric containing yarns or cellulosic fibers by means of such a composition.
  • the physico-chemical controls are carried out as follows: - the dry extract, expressed as a percentage by weight, is determined by drying 1 g of dispersion for 3 hours at 105 ° C; - the Brookfield viscosity is determined at 20-22 ° C with a Brookfield RVT viscometer equipped with axis 1 at the speed of 50 rpm; - the swelling rate, TG, is determined at room temperature by immersion in trichlorethylene of a circular flat test tube 50 mm in diameter cut from a dry film, about 0.5 mm thick, of the dispersion to test.
  • the TG is measured simultaneously on a film which has not been heat treated and on a film which has been treated for 10 minutes at 150 ° C.
  • the TG is calculated by the relation in which di is the initial diameter of the test piece and df, the final diameter; - the NMR spectra are determined on a Brucker AC 200 device (50 MHz 13C and 200 MHz 1H). The chemical shifts are expressed in ppm relative to tetramethylsilane.
  • the aqueous phase is washed twice with 355 g of diethyl ether and the ethereal phase is washed twice with 355 g of water.
  • Combined ethereal phases 156 g (1.1 mole) of unconverted glycidyl methacrylate are isolated after removal of the diethyl ether.
  • the combined aqueous phases are concentrated under vacuum to a total weight of 1140 g, designated hereinafter solution A.
  • 19 g (0.23 mole) of methoxyamine hydrochloride are introduced into 100 g of this solution A, then the solution obtained is left for 2 hours at room temperature.
  • a milky suspension is thus obtained which is washed twice with 136 g of dichloromethane, then the chloromethylenic phases are combined, dried over anhydrous magnesium sulfate and finally concentrated in vacuo.
  • 7.5 g of yellow oil are thus isolated and purified by preparative chromatography on a column (500 ⁇ 25) filled with silica with a particle size of 10 micrometers, with elution with a hexane-ethyl acetate mixture 8/2 by volume, which makes it possible to isolate on the one hand, 5 g (20, 4 mmol) of methacryloyloxy-1 methoxyiminoacetoxy-3 propanol-2 and, on the other hand, 2 g (8.15 mmol) of methacryloyloxy-3 methoxyiminoacetoxy-2 propanol-1 characterized by their NMR spectra1 recorded in deuterated chloroform.
  • solution A contains at least 50.28 g (0.23 mole) of methacryloyloxy-1 glyoxyloyloxy-3 propanol-2 and 20.1 g (93 mmol) of methacryloyloxy-3 glyoxyloyloxy-2 propanol-1 or 61% yield of the theory calculated with respect to the glyoxylic acid used.
  • Example 2 By operating as in Example 1, starting from 270.2 g (2.11 moles) of glycidyl acrylate, 48.8 g (0.53 moles) of glyoxylic acid monohydrate, 5.36 g (53 mmoles ) of triethylamine and 0.15 g of paramethoxyphenol, a mixture of acryloyloxy-1 glyoxyloyloxy-3 propanol-2 and acryloyloxy-3 glyoxyloyloxy-2 propanol-1 is obtained with a yield greater than 65% of the calculated theory compared to the glyoxylic acid used.
  • Example 2 By operating as in Example 1, starting from 300 g (2.63 moles) of allyl and glycidyl oxide, of 60.5 g (0.6575 mole) of glyoxylic acid monohydrate, of 6.6 g (66 mmol) of triethylamine and 150 mg of paramethoxyphenol, a mixture of allyloxy-1 glyoxyloyloxy-3 propanol-2 and allyloxy-3 glyoxyloyloxy-2 propanol-1 is obtained with a yield greater than 70% of the theory calculated with respect to the glyoxylic acid used.
  • a solution, designated S14, is prepared by dissolving, with stirring, at room temperature, in 199.6 g of distilled water: - 16.1 g of an aqueous solution at 28% by weight of the sodium salt of ethoxylated laurylethersulfate with 3 to 4 moles of ethylene oxide; - 33.8 g of an aqueous solution at 20% by weight of oleocetyl alcohol containing 25 moles of ethylene oxide; - 1 g of sodium hydrogen carbonate; - 1.2 g of potassium peroxodisulfate; - 2.61 g of methacrylamide.
  • a solution, designated S24 is prepared by mixing, with stirring, at room temperature: - 192.7 g of n-butyl acrylate; - 245.85 g of methyl methacrylate; - 2.25 g of acrylic acid; - 21.10 g of the Ac solution prepared in Example 1.
  • a fluid, milky, aqueous dispersion with a pH of 3.95 is obtained, a dry extract of 47.76%, a Brookfield viscosity of 50 mPa.s, a particle size (z-order average) of 172 nm, a swelling rate, TG, of 122% and a swelling rate of 110% after heat treatment.
  • a solution, designated S15 is prepared by dissolving, with stirring, at room temperature, in 273.6 g of distilled water: - 3.6 g of an aqueous solution at 50% by weight of sodium salt of ether sulfate of tributylphenol ethoxylated with 7 moles of ethylene oxide; - 4.5 g of an aqueous solution at 20% by weight of nonylphenol ethoxylated with 30 moles of ethylene oxide; - 0.9 g of ethoxylated nonylphenol with 6 moles of ethylene oxide; - 1 g of sodium hydrogen carbonate; - 2.61 g of methacrylamide; - 1.35 g of potassium peroxodisulfate.
  • a solution, designated S25 is prepared by mixing, with stirring, at room temperature: - 232.9 g of styrene; - 205.7 g of n-butyl acrylate; - 2.25 g of acrylic acid; - 21.10 g of the Ac solution prepared in Example 1.
  • the mixture is heated to 82 ° C., with stirring: - 250 g of distilled water; - 0.45 g of a 50% by weight aqueous solution of sodium salt of tributylphenol ethersulfate ethoxylated with 7 moles of ethylene oxide, then the solution obtained is added over 4 hours, with stirring, while maintaining the temperature at 84 ⁇ 1 ° C, by mixing the solutions S15 and S25 extemporaneously.
  • the reaction medium is maintained for one hour at 80 ° C. with stirring, then it is cooled to ambient temperature and finally, it is filtered through a 0.16 mm mesh opening sieve.
  • a solution, designated S16, is prepared by dissolving with stirring at room temperature in 209.7 g of distilled water: - 27 g of a 25% by weight aqueous solution of linear C14-C 18 sodium alkanesulfonate; - 11.25 g of an aqueous solution at 20% by weight of nonylphenol ethoxylated with 30 moles of ethylene oxide; - 11.25 g of an aqueous solution at 20% by weight of oleocetyl alcohol ethoxylated with 25 moles of ethylene oxide; - 0.68 g of sodium acetate; - 0.90 g of potassium peroxodisulfate; - 4.5 g of an aqueous solution at 29.7% by weight of sodium vinylsulfonate; - 2.61 g of methacrylamide.
  • a solution, designated S26 is prepared by mixing, with stirring, at room temperature: - 137.9 g of vinyl acetate; - 301.5 g of n-butyl acrylate; - 21.1 g of the Ac solution prepared in Example 1.
  • aqueous solution containing 0.45 g of potassium peroxodisulfate is successively introduced in 10 g of water, then one minute later, an aqueous solution containing 0.5 g of sodium metabisulfite in 10 g of water and finally, the solution is introduced over 4 hours with stirring, while maintaining the temperature at 84 ° C. obtained by extemporaneously mixing the previous solutions S16 and S26.
  • the reaction medium is maintained for one hour with stirring at 84 ° C. then it is cooled to room temperature and finally it is filtered through a 0.16 mm mesh opening sieve.
  • a solution designated S17 is prepared, dissolving with stirring at room temperature in 209.7 g of distilled water: - 27 g of an aqueous solution at 25% by weight of linear C14-C18 sodium alkanesulfonate; - 11.25 g of an aqueous solution at 20% by weight of nonylphenol ethoxylated with 30 moles of ethylene oxide; - 11.25 g of an aqueous solution at 20% by weight of oleocetyl alcohol ethoxylated with 25 moles of ethylene oxide; - 0.68 g of sodium acetate; - 0.90 g of potassium peroxodisulfate: - 4.5 g of an aqueous solution at 29.7% by weight of sodium vinylsulfonate; - 2.61 g of methacrylamide.
  • a solution, designated S27 is prepared by mixing, with stirring, at room temperature: - 137.9 g of vinyl acetate; - 301.5 g of n-butyl acrylate; - 4.4 g (31 mmol) of glycidyl methacrylate.
  • aqueous solution containing 0.45 g of potassium peroxodisulfate is successively introduced in 10 g of water, then one minute later, an aqueous solution containing 0.5 g of sodium metabisulfite in 10 g of water and finally, the mixture is introduced over 4 hours, with stirring, while maintaining the temperature at 84 ° C. aqueous solution obtained by extemporaneously mixing the previous solutions S17 and S27. At the end of introduction, the reaction medium is maintained for one hour with stirring at 84 ° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP89403447A 1989-02-23 1989-12-12 Glycerolderivate, ihr Herstellungsverfahren, diese enthaltende vernetzbare Zusammensetzungen und ihre Anwendung in der Textilindustrie Expired - Lifetime EP0384091B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89403447T ATE91484T1 (de) 1989-02-23 1989-12-12 Glycerolderivate, ihr herstellungsverfahren, diese enthaltende vernetzbare zusammensetzungen und ihre anwendung in der textilindustrie.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8902341 1989-02-23
FR8902341A FR2643368B1 (fr) 1989-02-23 1989-02-23 Nouveaux derives du glycerol, leur procede de preparation, compositions reticulantes en contenant, et leur utilisation dans l'industrie textile

Publications (2)

Publication Number Publication Date
EP0384091A1 true EP0384091A1 (de) 1990-08-29
EP0384091B1 EP0384091B1 (de) 1993-07-14

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EP89403447A Expired - Lifetime EP0384091B1 (de) 1989-02-23 1989-12-12 Glycerolderivate, ihr Herstellungsverfahren, diese enthaltende vernetzbare Zusammensetzungen und ihre Anwendung in der Textilindustrie

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US (1) US5093518A (de)
EP (1) EP0384091B1 (de)
JP (1) JPH02235847A (de)
AT (1) ATE91484T1 (de)
CA (1) CA2006804A1 (de)
DE (1) DE68907585T2 (de)
ES (1) ES2058583T3 (de)
FR (1) FR2643368B1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009026820A1 (de) * 2008-09-08 2010-03-11 Evonik Röhm Gmbh Funktionalisiertes (Meth)acrylatmonomer, Polymer, Beschichtungsmittel und Verfahren zur Herstellung und Vernetzung
WO2012143371A1 (de) 2011-04-18 2012-10-26 Momentive Performance Materials Gmbh Funktionalisierte polyorganosiloxane oder silane zur behandlung von lignocellulosischen werkstoffen
JP2018528289A (ja) 2015-07-20 2018-09-27 モメンティブ パフォーマンス マテリアルズ ゲーエムベーハー 非対称に置換されたポリオルガノシロキサン誘導体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4010183A (en) * 1975-03-28 1977-03-01 Scm Corporation Anhydrous solvent separation in production of polyol monoacylates
US4654370A (en) * 1979-03-12 1987-03-31 Abbott Laboratories Glyceryl valproates
US4990289A (en) * 1984-07-08 1991-02-05 Oncogen Biologically active lipids binding membrane receptors

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* Cited by examiner, † Cited by third party
Title
Eléments de la technique relevés: néant. *

Also Published As

Publication number Publication date
CA2006804A1 (en) 1990-08-23
FR2643368A1 (fr) 1990-08-24
ATE91484T1 (de) 1993-07-15
DE68907585T2 (de) 1993-10-28
FR2643368B1 (fr) 1991-06-07
EP0384091B1 (de) 1993-07-14
ES2058583T3 (es) 1994-11-01
DE68907585D1 (de) 1993-08-19
US5093518A (en) 1992-03-03
JPH02235847A (ja) 1990-09-18

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